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Linda, Luna's suggestion to use the Free Modifier Job Aid is a good one. Also, you probably should take the time to read through CPT Appendix A where the modifiers are described, then use the Modifier Grid to remind you of where the modifier fits in. You are correct that most modifiers are either intended for E/M OR for non-E/M procedures. Only modifiers -32 (mandated services) and -52 (reduced services) may be used with both E/M and non E/M procedures.
Regarding your other question: When a PT is seen in ER was assigned an E/M level and an IM was given, is it appropriate to add modifer -59 to the injection code? The answer is no, it is not appropriate. To use -59 you would need 2 non E/M procedures that are not normally reported together, and you only have one non E/M procedure (the injection).
It takes a while to learn how to use modifiers. A good medical coding course will provide you with lots of examples so you can understand when to use which modifier. CodingCertification.Org's Physician Based Medical Coding will provide a lot of examples and information regarding modifiers and other topics you will need to know to become certified.